Semi-aromatic polyamide with low melting temperature

Abstract

The invention relates to a polyamide (PA) exhibiting a melting temperature Tm strictly below 290 DEG C and comprising repeating units formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B), in which: c) the diamine component (A) comprises:-between 15.0 and 25.0 mol% of 1, 6-hexamethylenediamine; between 18.0 and 30.0 mol% of a diamine selected from the group consisting of 1, 9-diaminononane, 1, 10-diaminodecane, and a combination of said two diamines; between 50.0 and 64.0 mol% of a diamine selected from the group consisting of 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane and a combination of said two diamines; the proportions in mol% are based on the total amount of diamines in the diamine component (A); d) the dicarboxylic acid component (B) comprises:-between 95.0 and 100.0 mol% of terephthalic acid; between 0 and 5.0 mol% of another diacid selected from the group consisting of isophthalic acid, adipic acid and a combination of the two said diacids; the proportions in mol% are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

Description

[0001] This application claims priority to U.S. Patent Application No. 63 / 385,647, filed December 1, 2022, and European Patent Application No. 23154136.8, filed January 31, 2023, the contents of which are incorporated herein by reference in their entirety for all purposes. In the event of any inconsistency between the present application and those two (U.S. and European) applications that would affect the clarity of terminology or expression, reference shall be made solely to the present application. [Technical field]

[0002] The present invention relates to a semicrystalline, semiaromatic copolyamide having a combination of a high glass transition temperature and a low melting temperature and other properties that make it suitable for use in the preparation of thermoplastic composites. [Background Technology]

[0003] Aliphatic polyamides (such as the well-known PA6 and PA66) are a very popular class of thermoplastic resins because they are easy to process and generally have high melting points. They also exhibit high heat resistance values, especially when reinforced with fibers or fillers. However, when stored in water, they typically have high water absorption values ​​of up to 10%.

[0004] Aliphatic polyamides cannot be used in many applications with stringent requirements for dimensional stability (including wet or humid conditions). Water absorption alters not only the dimensions but also the mechanical properties. Water absorption reduces stiffness and strength to a fraction of their original values. However, there are many applications that involve mechanical loads in contact with water or ambient moisture.

[0005] Semiaromatic polyamides have been developed to address these issues. Trogamid T5000 is a commercial amorphous polyamide composed of terephthalic acid and a mixture of 2,2,4-TMD and 2,4,4-TMD. This polyamide is inherently amorphous and characterized by high mechanical strength and toughness. However, when exposed to temperatures above its Tg = 150°C (dry state) and in the presence of water, it loses all mechanical integrity due to a high moisture absorption rate of approximately 7.5 wt.%.

[0006] WO 2018 / 234439 discloses a polyamide BACT / 10T / 6T without disclosing any specific composition.

[0007] WO 2018 / 172717 discloses semiaromatic copolyamides with a BAC content of 1.3. The disclosed polyamides with a BAC content of 1.3 exhibit Tm values ​​above 290°C or are based on different compositions with higher BACT content. For example, WO 2018 / 172717 discloses a copolyamide 6T (25 mol%) / BACT (75 mol%) with a Tm of 306°C in Table III.

[0008] WO 2018 / 172718 discloses semi-aromatic copolyamides with a BAC of 1.3. The disclosed polyamides with a BAC of 1.3 exhibit a Tm above 290°C or are based on different compositions.

[0009] US2019 / 338074 (D1) and WO 2018 / 011495 disclose semiaromatic copolyamides based on 1.3BAC with a melting temperature below 300°C. The two compositions disclosed in the experimental sections of US2019 / 338074 and WO 2018 / 011495 are based on 10T, 6T, and BACT repeating units. The composition of claim 1 is not disclosed.

[0010] US2016 / 0152770 discloses a semiaromatic copolyamide comprising the following in copolymerized form: a) 36 to 50 mol% of terephthalic acid, b) 0 to 14 mol% of isophthalic acid, c) 35 to 42.5 mol% of hexamethylenediamine, and d) 7.5 to 15 mol% of at least one cyclic diamine, wherein the cyclic diamine d) comprises isophoronediamine. The proportion of hexamethylenediamine is higher than that in claim 1. Furthermore, bis(aminomethyl)cyclohexane is not mentioned.

[0011] US 2017 / 0107326 discloses polyamides having a higher proportion of 1,6-hexamethylenediamine and a higher melting temperature than in claim 1 .

[0012] WO 2021 / 037850 and US 2022 / 289909 (D3) disclose a polyamide formed from a diamine component (A) and a dicarboxylic acid component (B), wherein the diamine component (A) comprises 55 mol% to 75 mol% of a C4-C8 aliphatic diamine, 25 mol% to 45 mol% of a C9-C 12 aliphatic diamine, and 0 mol% to 10 mol% of alicyclic diamine containing a cyclohexyl group, the dicarboxylic acid component (B) comprises: 90 mol% to 100 mol% of terephthalic acid, 0 mol% to 10 mol% of C6-C 18 Aliphatic dicarboxylic acid or C8-C 18 An aromatic dicarboxylic acid and 0 to 10 mol% of an alicyclic dicarboxylic acid containing a cyclohexyl group. The proportion of 1,6-hexanediamine is higher than that in claim 1.

[0013] WO 2021 / 224431 discloses a polyamide formed by polycondensation of monomers in a reaction mixture comprising: 12A diamine component (A) of an aliphatic diamine and 5 to 80 mol% of bis(aminoalkyl)cyclohexane, and a dicarboxylic acid component (B) comprising 30 to 100 mol% of terephthalic acid and 0 to 70 mol% of cyclohexanedicarboxylic acid. WO 2021 / 224431 more specifically discloses a polyamide 6,T / 1,3-BAC,T / 6,CHDA / 1,3-BAC,CHDA having a Tm of 330°C.

[0014] WO 2022 / 180195 (D2) discloses a polyamide prepared from a diamine component comprising: 55 to 75 mol% of a C4-C8 diamine; 25 to 45 mol% of a C9-C 12 and 0 to 10 mol% of an alicyclic diamine containing a cyclohexyl group. Tm is higher than that of claim 1.

[0015] US2008 / 274355 (D4) discloses a copolyamide 10T / 6T, which is formed from the following components: a component (A1) having 40 to 95 mol % of 10T units; a component (A2) having 5 to 60 mol % of 6T units, with the proviso that, independently of one another, in (A1) and / or (A2), up to 30 mol % of terephthalic acid, based on the total dicarboxylic acids, can be replaced by other C6-C 36 The aromatic, aliphatic or cycloaliphatic dicarboxylic acids are replaced with aromatic, aliphatic or cycloaliphatic dicarboxylic acids, provided that in component (A), independently of one another, up to 30 mol % of 1,10-decanediamine and 1,6-hexanediamine, based on the total diamines, can be replaced by other C4-C 36 Diamine replacement. All examples are 10T / 6T copolyamide. D4 does not disclose the claimed copolyamide (PA).

[0016] [Technical Issues]

[0017] In the field of thermoplastic composites based on polyamides, a major challenge is to find resins that are easy to prepare, exhibit a high glass transition temperature (Tg) to allow the polyamide to be used in a wide range of operating temperatures, and a low melting temperature (Tm) to facilitate processing of the resin.

[0018] To prepare thermoplastic composites by melt infusion, resins are sought that have a low melt flow rate (meaning that the resin is easier to process in the melt) while maintaining a good balance of mechanical properties (chord modulus).

[0019] Resins with low crystallization temperatures (to reduce warpage and stress in the resin within the composite) and those that are sustainable are also being sought.

[0020] The polyamide of the present invention is intended to solve this technical problem.

[0021] [Brief Summary of the Invention]

[0022] The invention is set forth in the appended claims.

[0023] The present invention relates to a polyamide as disclosed in any one of claims 1 to 29.

[0024] The invention also relates to a thermoplastic composite material as defined in claim 30 .

[0025] The invention also relates to the use as defined in claim 31 .

[0026] More precise information and details on these topics are now provided below.

[0027] [definition]

[0028] These definitions apply to this disclosure.

[0029] wt% means % by weight and Mol% means % by mol.

[0030] Unless stated otherwise, the proportions of the recurring units in the polyamide are given in mol % and are relative to the total proportions of the recurring units in the polyamide.

[0031] When numerical ranges are given herein, the endpoints of those ranges (even open-ended ranges such as those including "at least," "at most," "less than," etc.) are included unless otherwise indicated.

[0032] In this application, unless otherwise indicated, any specific embodiment or technical feature relating to one of the subject matters of the present invention is applicable to and interchangeable with another embodiment or technical feature also relating to said subject matter and disclosed elsewhere in this application (especially in the claims).

[0033] The proportion of diamines in the diamine component (A) is expressed in mol % and is based on the total amount of diamines in the diamine component (A). The proportion of dicarboxylic acids in the dicarboxylic acid component (B) is expressed in mol % and is based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0034] The proportions of the repeating units in the polyamide (PA) are expressed in mol % and are based on the total amount of repeating units in the polyamide (PA).

[0035] Dicarboxylic acids are organic compounds containing two carboxyl groups (-COOH). [Specific implementation method]

[0036] The present invention relates to a semi-aromatic copolyamide (PA) exhibiting a melting temperature Tm strictly below 290° C. (<290° C.) and comprising repeating units formed by the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein:

[0037] a) The diamine component (A) comprises:

[0038] - between 15.0 and 25.0 mol % of 1,6-diaminohexane;

[0039] - between 18.0 and 30.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0040] - between 50.0 and 64.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0041] These proportions in mol % are based on the total amount of diamines in the diamine component (A);

[0042] b) the dicarboxylic acid component (B) comprises:

[0043] - between 95.0 and 100.0 mol % of terephthalic acid;

[0044] - between 0 and 5.0 mol% of another diacid (DI) chosen from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids;

[0045] These proportions in mol % are based on the total amount of diacids in the dicarboxylic acid component (B).

[0046] The present invention also relates to a semi-aromatic copolyamide (PA) exhibiting a melting temperature Tm strictly below 290° C. (<290° C.) and comprising repeating units formed by the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein:

[0047] a) The diamine component (A) comprises:

[0048] - between 15.0 and 25.0 mol % of 1,6-diaminohexane;

[0049] - between 18.0 and 30.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0050] - between 50.0 and 62.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0051] These proportions in mol % are based on the total amount of diamines in the diamine component (A);

[0052] b) the dicarboxylic acid component (B) comprises:

[0053] - between 95.0 and 100.0 mol % of terephthalic acid;

[0054] - between 0 and 5.0 mol% of another diacid (DI) chosen from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids;

[0055] These proportions in mol % are based on the total amount of diacids in the dicarboxylic acid component (B).

[0056] The polyamide (PA) of the present invention is formed by polycondensation of the diamines in the diamine component (A) and one or more diacids in the dicarboxylic acid component (B). Therefore, the proportion of -NH2 from the diamines of the diamine component (A) and the proportion of -COOH from the dicarboxylic acids of the dicarboxylic acid component (B) are substantially equimolar. The molar ratio of -NH2 from the diamines of the diamine component (A) / -COOH from the dicarboxylic acids of the dicarboxylic acid component (B) is preferably between 0.9 and 1.1, preferably between 0.95 and 1.05, and even more preferably between 0.98 and 1.02.

[0057] The polyamide (PA) disclosed in the present invention therefore comprises the diamines of the diamine component (A) and the dicarboxylic acids of the dicarboxylic acid component (B) in reacted form in the ratios indicated therein.

[0058] More details are now provided regarding the diamine component (A) and the dicarboxylic acid component (B).

[0059] About diamine component (A)

[0060] The diamine component (A) is based on and comprises the following diamines: 1,6-diaminohexane (having the formula NH2-(CH2)6-NH2); a diamine selected from the group consisting of 1,9-diaminononane (having the formula NH2-(CH2)9-NH2), 1,10-diaminodecane (having the formula NH2-(CH2) 10 -NH2) and a combination of the two diamines (D1); and bis(aminomethyl)cyclohexane (D2).

[0061] The proportion of 1,6-diaminohexane is between 15.0 and 25.0 mol %. This proportion may more particularly be between 15.0 and 20.0 mol % or between 15.0 and 22.0 mol % or between 18.0 and 22.0 mol %.

[0062] The diamine component (A) further comprises another diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, and a combination of these two diamines. This diamine (D1) can more particularly be 1,9-diaminononane. This diamine (D1) can also more particularly be 1,10-diaminodecane. The proportion of the one or more other diamines (D1) is between 18.0 and 30.0 mol %, or between 18.0 and 27.0 mol %. This proportion of D1 can more particularly be between 23.0 and 27.0 mol %, or between 18.0 and 22.0 mol %.

[0063] The diamine component (A) further comprises bis(aminomethyl)cyclohexane (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane (1,4-BAC), and a combination of the two diamines. 1,3-bis(aminomethyl)cyclohexane is a diamine having the formula: 1,4-Bis(aminomethyl)cyclohexane is a diamine having the formula: The diamine (D2) may more particularly and preferably be 1,3-bis(aminomethyl)cyclohexane. The diamine (D2) may more particularly be 1,4-bis(aminomethyl)cyclohexane. The proportion of the one or more other diamines (D2) may be between 50.0 and 64.0 mol % or between 50.0 and 62.0 mol %. This proportion of D2 may more particularly be between 53.0 and 62.0 mol % or between 53.0 and 57.0 mol % or between 58.0 and 62.0 wt % or between 61.0 and 64.0 mol %.

[0064] According to embodiment (E1), the ratios in the diamine component (A) are the following:

[0065] - between 18.0 and 22.0 mol % of 1,6-diaminohexane;

[0066] - between 23.0 and 27.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0067] - between 53.0 and 57.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0068] These proportions in mol % are based on the total amount of diamines in the diamine component (A).

[0069] According to another embodiment (E2), the ratio of the diamine component (A) is the following ratio:

[0070] - between 18.0 and 22.0 mol % of 1,6-hexanediamine;

[0071] - between 18.0 and 22.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0072] - between 58.0 and 62.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0073] These proportions in mol % are based on the total amount of diamines in the diamine component (A).

[0074] According to another embodiment (E3), the ratio of the diamine component (A) is the following ratio:

[0075] - between 15.0 and 20.0 mol % of 1,6-hexanediamine;

[0076] - between 18.0 and 22.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0077] - between 61.0 and 64.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0078] These proportions in mol % are based on the total amount of diamines in the diamine component (A).

[0079] All details and examples disclosed in this disclosure apply to any of embodiments (E1)-(E3).

[0080] According to an embodiment, the diamine component (A) consists essentially of or consists of 1,6-diaminohexane; a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, and a combination of the two diamines; and a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, and a combination of the two diamines, in the proportions indicated herein.

[0081] The expression "essentially consists of" means that in the context of the present invention in connection with the diamine component (A), the diamine component (A) comprises the indicated diamine and may also comprise up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diamine other than the indicated diamine, the proportion in mol % being based on the total amount of diamines in the diamine component (A). Thus, the diamine component (A) consists of: 1,6-diaminohexane; a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of the two diamines; a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of the two diamines; and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diamine other than 1,6-diaminohexane, D1 and D2, the proportions in mol % being based on the total amount of diamines in the diamine component (A).

[0082] The diamine component (A) may preferably be based on the following combination of diamines: 1,6-diaminohexane+(1,9-diaminononane and / or 1,10-diaminodecane)+1,3-bis(aminomethyl)cyclohexane. According to an embodiment, the diamine component (A) consists essentially of or consists of [1,6-diaminohexane+1,9-diaminononane and / or 1,10-diaminodecane+1,3-bis(aminomethyl)cyclohexane], wherein the expression "consisting essentially of" means that the diamine component (A) consists of: 1,6-diaminohexane; 1,9-diaminononane and / or 1,10-diaminodecane; 1,3-bis(aminomethyl)cyclohexane; and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diamine other than 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane and 1,3-bis(aminomethyl)cyclohexane, the proportions in mol % being based on the total amount of diamines in the diamine component (A).

[0083] The diamine component (A) may be based on the following diamine combination: 1,6-diaminohexane+(1,9-diaminononane and / or 1,10-diaminodecane)+1,4-bis(aminomethyl)cyclohexane in the proportions indicated herein. According to an embodiment, the diamine component (A) consists essentially of or consists of [1,6-diaminohexane+1,9-diaminononane and / or 1,10-diaminodecane+1,4-bis(aminomethyl)cyclohexane], wherein the expression "consisting essentially of" means that the diamine component (A) consists of: 1,6-diaminohexane; 1,9-diaminononane and / or 1,10-diaminodecane; 1,4-bis(aminomethyl)cyclohexane; and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diamine other than 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane and 1,4-bis(aminomethyl)cyclohexane, the proportion in mol % being based on the total amount of diamines in the diamine component (A).

[0084] About dicarboxylic acid component (B)

[0085] The dicarboxylic acid component (B) is based on terephthalic acid as the main component of the dicarboxylic acid component (B).The dicarboxylic acid component (B) may further comprise another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid and a combination of the two diacids.

[0086] The dicarboxylic acid component (B) comprises:

[0087] - between 95.0 and 100.0 mol % of terephthalic acid;

[0088] - between 0 and 5.0 mol% of another diacid (DI) chosen from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids;

[0089] These proportions in mol % are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0090] These proportions may more particularly be proportions of between 95.0 and 99.9 mol% of terephthalic acid and between 0.1 and 5.0 mol% of the other diacid(s) (DI).

[0091] These proportions may more particularly be proportions of between 98.0 and 99.9 mol% of terephthalic acid and between 0.1 and 5.0 mol% of the other diacid(s) (DI).

[0092] The diacid (DI) other than terephthalic acid may more particularly be isophthalic acid.

[0093] The diacid (DI) other than terephthalic acid may more particularly be adipic acid.

[0094] The proportions in the dicarboxylic acid component (B) may more particularly be the following proportions:

[0095] - between 98.0 and 100.0 mol % of terephthalic acid;

[0096] - between 0 and 2.0 mol% of another diacid (DI) chosen from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids;

[0097] These proportions in mol % are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0098] These proportions may more particularly be proportions of between 98.0 and 99.9 mol% of terephthalic acid and between 0.1 and 2.0 mol% of the other diacid(s) (DI).

[0099] According to an embodiment, the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and the diacid (DI). The expression "consists essentially of" means that in the context of the present invention with respect to the dicarboxylic acid component (B), the dicarboxylic acid component (B) consists of terephthalic acid, the diacid (DI) and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diacid other than terephthalic acid and the diacid DI, the proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0100] The diamine component (A) and the dicarboxylic acid component (B) preferably do not contain lactams. The diamine component (A) and the dicarboxylic acid component (B) preferably do not contain amino acids. The diamine component (A) and the dicarboxylic acid component (B) preferably do not contain isophoronediamine.

[0101] Example (E):According to a preferred embodiment (E), the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid. The expression "consists essentially of" means that in the context of the present invention in connection with embodiment (E) and the dicarboxylic acid component (B), the dicarboxylic acid component (B) comprises terephthalic acid and may also comprise up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol %, of at least one further diacid other than terephthalic acid, the proportion in mol %, being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B). Thus, the dicarboxylic acid component (B) consists of terephthalic acid and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol %, of at least one further diacid other than terephthalic acid, the proportion in mol %, being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0102] All details and examples disclosed in this disclosure apply to Example (E).

[0103] Under embodiment (E), the skilled person understands that polyamide (PA) can be described as comprising the following repeating units (R PA1 )、(R PA2 ) and (R PA3 ):

[0104]

[0105] and / or

[0106]

[0107] or the following repeating units (R PA1 )、(R PA2 ) and (R PA3 ):

[0108]

[0109] wherein R1 is hexamethylene -(CH2)6-, and R2 is a divalent radical of a diamine selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, and a combination of the two diamines. For clarity, the divalent radical of 1,9-diaminononane is -(CH2)9-, and the divalent radical of 1,10-diaminodecane is -(CH2) 10 .

[0110] R PA1 corresponds to the repeating unit obtained by the reaction of terephthalic acid with 1,6-diaminohexane, and R PA2corresponds to the repeating units obtained from the reaction of terephthalic acid with the one or more other diamines in C9 and / or C10. Similarly, R PA3 corresponds to the repeating units obtained from the reaction of terephthalic acid with bis(aminomethyl)cyclohexane (eg, 1,3-bis(aminomethyl)cyclohexane and / or 1,4-bis(aminomethyl)cyclohexane).

[0111] All ratios and examples given herein for the ratios of the diamines in the diamine component (A) apply here.

[0112] Therefore, the ratios in the repeating units may be as follows:

[0113] -R PA1 : between 15.0 and 25.0 mol%;

[0114] -R PA2 : between 18.0 and 30.0 mol%;

[0115] -R PA3 : between 50.0 and 64.0 mol %;

[0116] or the following ratio:

[0117] -R PA1 : between 15.0 and 25.0 mol%;

[0118] -R PA2 : between 18.0 and 30.0 mol%;

[0119] -R PA3 : between 50.0 and 62.0 mol%;

[0120] These proportions in mol % are relative to the total amount of repeating units in the polyamide (PA).

[0121] According to an embodiment, the repeating unit (R PA1 )、(R PA2 ) and (R PA3 ) is at least 95.0 mol %, more particularly at least 99.0 mol %. According to another embodiment, the recurring units of the polyamide (PA) consist essentially of these recurring units (R PA1 )、(R PA2 ) and (R PA3 ). The expression "essentially consists of" in relation to the repeating units of polyamide (PA) means that the repeating units of the polyamide consist of (R PA1 )、(R PA2 ) and (R PA3) and up to 2.0 mol%, preferably up to 1.5 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol% of other than the repeating unit (R PA1 )、(R PA2 ) and (R PA3 ) other than the repeating units.

[0122] R PA1 The proportion of is between 15.0 and 25.0 mol %. This proportion may more particularly be between 15.0 and 20.0 mol % or between 15.0 and 22.0 mol % or between 18.0 and 22.0 mol %.

[0123] R PA2 The proportion of is between 18.0 and 30.0 mol % or between 18.0 and 27.0 mol %. This proportion may more particularly be between 23.0 and 27.0 mol % or between 18.0 and 22.0 mol %.

[0124] R PA3 The proportion of is between 50.0 and 64.0 mol % or between 50.0 and 62.0 mol %. This proportion may more particularly be between 53.0 and 62.0 mol % or between 53.0 and 57.0 mol % or between 58.0 and 62.0 wt % or between 61.0 and 64.0 mol %.

[0125] According to an embodiment, these ratios are the following ratios:

[0126] - between 15.0 and 25.0 mol% of R PA1 ;

[0127] - between 23.0 and 27.0 mol% of R PA2 ;

[0128] - between 53.0 and 57.0 mol% of R PA3 .

[0129] According to another embodiment, these ratios are the following ratios:

[0130] - between 15.0 and 25.0 mol% of R PA1 ;

[0131] - between 18.0 and 22.0 mol% of R PA2 ;

[0132] - between 58.0 and 62.0 mol% of R PA3 .

[0133] The polyamide (PA) of the present invention preferably comprises no repeating units derived from lactams or from amino acids.The polyamide (PA) of the present invention preferably comprises no repeating units derived from isophoronediamine.

[0134] The polyamide (PA) of the present invention typically has a number average molecular weight ("Mn") in the range of 1,000 g / mol to 40,000 g / mol, for example 2,000 g / mol to 35,000 g / mol, 4,000 to 30,000 g / mol, or 5,000 g / mol to 20,000 g / mol. Mn can also be between 8,000 and 20,000 g / mol. Mn is preferably strictly above 8,000 g / mol. Mn can be determined by size exclusion chromatography (SEC) using polystyrene standards or by using the following equation (1): Mn=2,000,000 / [EG] (1), where [EG] is the proportion of end groups in the polyamide (PA) (expressed in mmol / kg), more precisely determined using known methods for measuring the concentration of amine end groups and the concentration of acid end groups. The end groups in the polyamide (PA) are typically amine and / or acid moieties. However, when the polycondensation involves the addition of an end-capping agent, the amine end groups are partially or completely converted into one or more modified end groups. For example, when the end-capping agent is an acid such as benzoic acid or acetic acid, the remaining amine groups can be converted in whole or in part into benzamide or acetamide end groups.

[0135] The end groups in the polyamide (PA) are selected from the group consisting of -NH2, -COOH and amide end groups. In fact, the end groups in the polyamide (PA) can be -NH2 or -COOH. However, when the polycondensation involves the addition of an end-capping agent, these end groups can be partially or completely converted into amide end groups.

[0136] The amide end groups are of the formula -NH-C(=O)-R, wherein R is an alkyl, aryl or cycloalkyl group, and / or of the formula -C(=O)-NH-R', wherein R' is an alkyl or cycloalkyl group. R is more particularly a linear or branched C1-C 17 Alkyl or C5-C 10 Cycloalkyl. R' is more particularly a linear or branched C2-C 18 alkyl.

[0137] Amide end groups of the formula -NH-C(=O)-R are produced by the reaction of the end group -NH2 with a monocarboxylic acid of the formula R-COOH (capping agent).

[0138] The monocarboxylic acid (capping agent) may advantageously be selected from the group consisting of: benzoic acid; cyclohexanoic acid; R-COOH, wherein R is a linear or branched C1-C 17and combinations of two or more of these acids. R is a group derived from an acid having the formula R-COOH.

[0139] The monocarboxylic acid (capping agent) may more particularly be chosen from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid and combinations of two or more of these acids.

[0140] The monocarboxylic acid (capping agent) is more particularly a monocarboxylic acid having the formula CH3-(CH2) n -COOH, wherein n is an integer between 0 and 16. The amide end group has the formula -NH-C(=O)-(CH2) n -CH3.

[0141] An amide end group of formula -C(=O)-NH-R' results from the reaction of a terminal group -COOH with a primary amine of formula R'-NH2 (capping agent).

[0142] The primary amine (capping agent) may advantageously be selected from the group consisting of: amines having the formula R'-NH2, wherein R' is a linear or branched C2-C 18 Alkyl. R' is a group derived from an amine having the formula R'-NH2.

[0143] The primary amine (capping agent) is more particularly a amine having the formula CH3-(CH2) n' -NH2, wherein n' is an integer between 2 and 18. The amide end group is of the formula -C(=O)-NH-(CH2) n' -CH3.

[0144] The primary amine (blocking agent) may more particularly be chosen from the group consisting of propylamine, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine and combinations of two or more of these amines.

[0145] The proportion of end groups in polyamide (PA) can be determined by 1 Quantification was by H NMR or potentiometry techniques.

[0146] The polyamide (PA) preferably exhibits an inherent viscosity ("IV") measured according to ASTM D5336 of between 0.5 and 1.5 dL / g, more particularly between 0.7 and 1.3 dL / g, more particularly between 0.75 and 1.20 dL / g. The IV may be between 0.80 and 1.00 dL / g or between 0.90 and 1.20 dL / g. The IV may be conveniently measured in a 60 wt% / 40 wt% phenol / tetrachloroethane mixture.

[0147] The polyamide (PA) advantageously exhibits a melt flow rate (MFR) lower than or equal to 6.0 g / 10 min, preferably lower than or equal to 5.0 g / 10 min, preferably lower than or equal to 4.0 g / 10 min, preferably lower than or equal to 3.0 g / 10 min, the MFR being measured according to ASTM D1238 using a 2.16 kg test load at Tm+20° C. The measurement conditions given in the experimental part may be followed.

[0148] Polyamide (PA) can be prepared from the combinations of monomers as disclosed in Table I or Table II.

[0149] Moisture absorption rate

[0150] The polyamide (PA) advantageously exhibits a water absorption at 23°C of less than 5.0 wt%.

[0151] The water absorption at 23° C. is determined by (i) providing a test specimen formed according to ISO 527 in its dry state (moisture content less than 0.2 wt.%), (ii) immersing the test specimen in deionized water at 23° C. until constant weight is reached, and (iii) calculating the water absorption using the following formula:

[0152]

[0153] Where W 之前 is the weight of the molded specimen in its initial dry state and W 之后 is the weight of the molded specimen after water absorption.

[0154] Biomass content

[0155] The polyamide (PA) may exhibit a biocontent of at least 10.0%.The biocontent is expressed as a % of organic carbon of renewable origin determined according to ASTM D6866-22.

[0156] The biocontent is preferably at least 12.0%.The biocontent may be between 10.0% and 20.0%.

[0157] Biocontent is defined as the % of organic carbon of renewable origin. It corresponds to the 14 The amount of C is calculated from the C percentage and corrected for the isotope fraction.

[0158] Both the C9 and C10 diamines used to make polyamide (PA) can be bio-based or produced from petroleum or natural gas:

[0159]

[0160] Therefore, the polyamide (PA) disclosed herein is preferably prepared from bio-based 1,9-diaminononane (C9) and / or 1,10-diaminodecane (C10). This allows for the production of polyamide (PA) with a high biocontent. The high biocontent of PA comes primarily from C9 and / or C10 diamines.

[0161] According to an embodiment, the polyamide (PA) disclosed herein is prepared from 1,9-diaminononane (C9) and / or 1,10-diaminodecane (C10), which exhibits a biocontent of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, the biocontent being expressed as a % of organic carbon of renewable origin measured according to ASTM D6866-22.

[0162] However, the biocontent can also be increased by using bio-based terephthalic acid. Bio-based terephthalic acid can be produced, for example, from bio-based furfural, as described in Tachibana, Y., Kimura, S. & Kasuya, K.-i. "Synthesis and Verification of Biobased Terephthalic Acid from Furfural," Sci. Rep. 5, 8249; DOI: 10.1038 / srep08249 (2015). The biocontent, as defined above, can then be at least 60.0%.

[0163] Thermal properties of polyamide (PA)

[0164] As indicated above, it has surprisingly been found that the polyamides (PA) of the present invention exhibit a combination of thermal properties.Any of the features of thermal properties disclosed below may be used to characterize the polyamides of the present invention.

[0165] 1) Melting point (Tm)

[0166] The polyamide exhibits a Tm strictly below 290°C (<290°C). The Tm may be below 285°C or below 280°C or below 270°C.

[0167] Tm is generally at least 250°C, preferably at least 260°C.

[0168] The Tm may be between 250°C and 290°C or between 250°C and 280°C.

[0169] Tm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using heating and cooling rates of 20°C / min.

[0170] Tm can be measured more particularly as described in the experimental part.

[0171] Tm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C. Tm is determined from the second heat.

[0172] 2) Glass transition temperature (Tg)

[0173] The polyamide (PA) exhibits a Tg of at least 155° C. The Tg of the polyamide (PA) may preferably be at least 165° C., preferably at least 166° C., preferably at least 167° C., preferably at least 168° C., preferably at least 169° C., preferably at least 170° C.

[0174] Polyamide (PA) typically exhibits a Tg of at most 200°C or at most 180°C.

[0175] The Tg may more particularly be between 155 and 180°C or between 165 and 180°C.

[0176] Tg can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using heating and cooling rates of 20°C / min.

[0177] Tg can be measured more particularly as described in the experimental part.

[0178] Tg can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C. Tg is determined from the second heat.

[0179] According to a preferred embodiment, the polyamide (PA) exhibits a difference (Tm-Tg) below 130°C, preferably below 120°C, preferably below 110°C, preferably below 100°C.

[0180] 3) Heat of fusion (Hm)

[0181] Polyamide (PA) is semi-crystalline.

[0182] The polyamide (PA) exhibits a Hm of at least 15.0 J / g, preferably at least 20.0 J / g, preferably at least 25.0 J / g.

[0183] Hm may be lower than or equal to 40.0 J / g (≤40.0 J / g). Hm may more particularly be at most 39.0 J / g.

[0184] Hm is more particularly between 15.0 and 40.0 J / g, more particularly between 15.0 and 40.0 J / g (this latter value being excluded).

[0185] Hm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using heating and cooling rates of 20°C / min.

[0186] Hm can be measured more particularly as described in the experimental section. In fact, Hm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C.

[0187] Hm can be measured as described in the experimental section.

[0188] 4) Crystallization temperature (Tc)

[0189] Polyamide (PA) exhibits a Tc of up to 210°C.

[0190] Tc is usually at least 180°C.

[0191] Tc may be between 180°C and 210°C.

[0192] Tc is measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using heating and cooling rates of 20°C / min.

[0193] Tc can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C. Tc is determined from the first cooling.

[0194] The lower the Tc, the better for the preparation of thermoplastic composites, because the lower Tc helps to minimize warpage and stress in the resin. The polyamide (PA) of the present invention preferably exhibits a (Tm-Tc) of at least 50.0°C, preferably at least 60.0°C. (Tm-Tc) may be between 50.0°C and 75.0°C or between 50.0°C and 70.0°C.

[0195] Method for preparing polyamide (PA)

[0196] The polyamides (PA) described herein can be prepared by any conventional method suitable for the synthesis of polyamides and polyphthalamides.

[0197] Polyamide (PA) is produced by polycondensation.

[0198] Polyamide (PA) can be prepared by heating a reaction mixture (RM) comprising all monomers constituting the polyamide (PA) [e.g., hexamethylenediamine, D1 and D2, terephthalic acid, and optionally DI], preferably in the presence of less than 60 wt.%, preferably less than 30 wt.%, less than 20 wt.%, less than 10 wt.% of water, preferably without adding water. The proportions are based on the total weight of the reaction mixture (RM).

[0199] The temperature to which the reaction mixture (RM) is heated must be high enough to initiate the reaction between the amine groups and the carboxyl groups and to reduce the viscosity of the reaction mixture. This temperature is generally at least 200° C. The reaction mixture (RM) is preferably heated at a temperature ≥ Tm + 25° C. Polycondensation results in the formation of amide bonds and the release of water as a by-product.

[0200] The reaction mixture (RM) comprises the diamines of the diamine component (A) and the one or more diacids of the dicarboxylic acid component (B). As detailed above, the ratio of the two components is such that the reaction mixture contains an amount of monomers such that the ratio of -COOH groups from the dicarboxylic acid and the ratio of -NH2 groups from the diamine are substantially equimolar. The molar ratio of -NH2 from the diamines of the diamine component (A) / -COOH from the dicarboxylic acid of the dicarboxylic acid component (B) is preferably between 0.9 and 1.1, preferably between 0.95 and 1.05, and even more preferably between 0.98 and 1.02.

[0201] Reaction mixture (RM) preferably further comprises catalyzer.Catalyzer can be selected from the group consisting of: phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid, the acid and the salt of monovalent to trivalent cation and the ester of the acid.Cation can for example be Na, K, Mg, Ca, Zn or Al.The example of ester is triphenyl phosphate, triphenyl phosphite and tris (nonylphenyl) phosphite.The catalyzer conveniently used is phosphorous acid.

[0202] The proportion of catalyst in the reaction mixture (RM) is preferably between 0.005 and 2.5 wt%, based on the weight of the monomers in the reaction mixture.

[0203] According to embodiments of the present disclosure, the reaction mixture (RM) comprises or consists of:

[0204] - monomers constituting polyamide (PA), as disclosed herein;

[0205] - optionally a catalyst, in particular chosen from the group consisting of phosphorous acid, orthophosphoric acid, metaphosphoric acid, alkali metal hypophosphites such as sodium hypophosphite, and phenylphosphinic acid, and combinations thereof;

[0206] - optionally at least one capping agent selected from the group consisting of monocarboxylic acids, primary amines, and combinations thereof;

[0207] - Water, in a proportion of less than 60 wt.%, preferably less than 30 wt.%, preferably less than 20 wt.%, preferably less than 10 wt.% of water, the proportion being based on the total weight of the reaction mixture (RM). According to an embodiment, no water is added at the start of the polycondensation.

[0208] In order to control the molar mass, at least one chain transfer agent can be used, which is preferably selected from the group consisting of C1-C 18 Monocarboxylic acids and C3-C 18 The chain transfer agent may more particularly be chosen from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine, and mixtures thereof.

[0209] The polycondensation is advantageously carried out in a well-stirred vessel equipped with a device for removing the volatile products of the reaction. As the viscosity of the reaction mixture increases over time, the stirrer is suitable for providing sufficient stirring for the reaction mixture (RM) at the beginning of the polymerization and when the polycondensation conversion is nearing completion.

[0210] The conditions disclosed in the experimental section can be conveniently used to prepare polyamide (PA).

[0211] Thermoplastic Composites (TC)

[0212] The polyamide (PA) of the present invention is suitable for preparing a thermoplastic composite (TC), which comprises:

[0213] a polymer matrix comprising or consisting of at least one polyamide (PA) and optionally at least one plastic additive; and

[0214] -fiber.

[0215] The proportion of fibers in the thermoplastic composite (TC) is generally at least 40.0 wt%.

[0216] Thermoplastic composites (TC) comprise or consist of a polymer matrix and fibers. The fibers are adhesively or polymerically bonded to the matrix, which typically completely surrounds the fibers.

[0217] The polymer matrix comprises the polyamide (PA) of the present invention and optionally at least one plastic additive blended with the polyamide. The plastic additive may be selected from the group consisting of colorants (e.g., dyes and / or pigments), UV stabilizers, heat stabilizers, antioxidants, acid scavengers, processing aids, internal and / or external lubricants, flame retardants, smoke suppressants, antistatic agents, anti-caking agents, and any combination thereof. The proportion of the one or more plastic additives in the polymer matrix is ​​typically less than 20.0 wt%, based on the total weight of the polymer matrix.

[0218] Fibers generally exhibit high specific stiffness and strength values.

[0219] The fibers may be of inorganic type (eg glass fibers) or of organic type (eg aramid fibers or carbon fibers). Combinations of various fibers may also be used.

[0220] The fibers may be selected from the group consisting of glass fibers, carbon fibers, aramid fibers, stainless steel fibers, potassium titanate whiskers, and combinations of two or more thereof.

[0221] Thermoplastic composites (TC) can be manufactured by methods well known in the art. Generally, regardless of the type of method, composite material manufacturing includes impregnating fibers with a polymer matrix in molten form and then cooling to room temperature. Melt impregnation may further include mechanical compression of the melt on the fibers.

[0222] Thermoplastic composites (TC) can be used to prepare articles for the automotive industry.

[0223] [Experimental part]

[0224] The examples of the present invention illustrate the synthesis, thermal properties and mechanical properties of polyamides. The raw materials used to form the samples are provided below:

[0225] Raw materials used

[0226] The following raw materials were used to prepare the polyamide:

[0227] Table I

[0228]

[0229] Thermal performance

[0230] Tg, Tm, and Hm are measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C. Tg, Tm, and Hm are determined from the second heating. Tc is determined from the first cooling.

[0231] Inherent viscosity (IV)

[0232] Inherent viscosity (IV) was measured according to ASTM D5336 in a 60 wt% phenol-40 wt% tetrachloroethane mixture.

[0233] Melt flow rate (MFR)

[0234] Measured according to ASTM D 1238 using a 2.16 kg test load. Prior to testing, samples were dried at 225°F for 24 hours.

[0235] Chordal modulus

[0236] Measured according to ISO 527 using ISO 1A strips.

[0237] Biomass content

[0238] Determined according to ASTM D6866-22.

[0239] Preparation of polyamide

[0240] All copolyamides disclosed in Table II were prepared in an autoclave reactor equipped with a distillate line equipped with a pressure control valve.

[0241] All copolyamides were prepared by charging the monomers, water and phosphorous acid in the targeted ratios into a reactor and following the procedure given in Example 1 below.

[0242] Example 1 (E1):Polyamide E1 was prepared by charging a reactor with 0.79 g of hexamethylenediamine, 1.46 g of 1,10-diaminodecane, 2.65 g of 1,3-cyclohexane-bis(methylamine), 5.32 g of terephthalic acid, 5.04 g of deionized water, and 0.0034 g of phosphorous acid. The reactor was sealed and purged three times with N2 gas. The reactor was heated to 177°C and held for 30 minutes, then heated to 232°C and held for 30 minutes, then heated to 288°C and held for 30 minutes, then heated to 343°C and held for 35 minutes. The steam generated was slowly released to maintain the internal pressure below 200 psig. Once the temperature was maintained at 343°C for 35 minutes, the reactor pressure was slowly reduced to atmospheric pressure over 25 minutes. After the decompression was completed, the reactor was continuously purged with N2 gas over 25 minutes. Afterwards, the reactor was cooled to room temperature and the polymer was removed from the reactor.

[0243] As can be seen from the results in Table II, the specific ratio of monomers allows for a balance of properties, particularly a high Tg and a low Tm.

[0244] Furthermore, the polyamides of the present invention exhibit a balance of MFR and IV at Tm+20°C.

[0245]

[0246]

Claims

1. A polyamide (PA) exhibiting a melting temperature Tm strictly below 290° C. and comprising repeating units formed by the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein: a) The diamine component (A) comprises: - between 15.0 and 25.0 mol % of 1,6-hexanediamine; - between 18.0 and 30.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 50.0 and 64.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines; These proportions in mol % are based on the total amount of diamines in the diamine component (A); as well as b) the dicarboxylic acid component (B) comprises: - between 95.0 and 100.0 mol % of terephthalic acid; - between 0 and 5.0 mol% of another diacid (DI) chosen from the group consisting of isophthalic acid, adipic acid and a combination of these two said diacids; These proportions in mol % are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

2. The polyamide (PA) according to claim 1, wherein The diamine component (A) consists essentially of or consists of 1,6-diaminohexane; a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of the two diamines; and a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of the two diamines, the expression "essentially consisting of" meaning that the diamine component (A) consists of 1,6-diaminohexane, D1 and D2 and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol %, of at least one further diamine other than 1,6-diaminohexane, D1 and D2, the proportions in mol % being based on the total amount of diamines in the diamine component (A).

3. The polyamide (PA) according to claim 1 or claim 2, wherein The dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and the one or more other diacids (DI), expressed as "Essentially consisting of" means that the dicarboxylic acid component (B) consists of terephthalic acid, diacid (DI) and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diacid other than terephthalic acid and one or more diacids (DI), the proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

4. The polyamide according to claim 1 or claim 2, wherein The dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid, "Essentially consisting of" means that the dicarboxylic acid component (B) consists of terephthalic acid and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diacid other than terephthalic acid, the proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

5. The polyamide (PA) according to any one of claims 1 to 3, wherein The ratios in the dicarboxylic acid component (B) are the following ratios: - between 95.0 and 99.9 mol % of terephthalic acid and between 0.1 and 5.0 mol % of the other diacid(s) (DI); or - between 98.0 and 99.9 mol % of terephthalic acid and between 0.1 and 2.0 mol % of the other diacid(s) (DI).

6. A polyamide (PA), in particular a polyamide (PA) according to any one of the preceding claims, comprising repeating units (R PA1 )、(R PA2 ) and (R PA3 ): and / or or the following repeating units: wherein R1 is -(CH2)6-, and R2 is a divalent radical of a diamine selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, and a combination of the two diamines; The ratios in the repeating units are the following: -R PA1 : between 15.0 and 25.0 mol%; -R PA2 : between 18.0 and 30.0 mol%; -R PA3 : between 50.0 and 64.0 mol %; These proportions in mol % are relative to the total amount of repeating units in the polyamide (PA).

7. The polyamide (PA) according to claim 6, wherein Repeating unit (R PA1 )、(R PA2 ) and (R PA3 ) is at least 95.0 mol %, more particularly at least 99.0 mol %.

8. The polyamide (PA) according to claim 6, wherein The repeating units of the polyamide (PA) consist essentially of repeating units (R PA1 )、(R PA2 ) and (R PA3 ) The expression "essentially consists of" in relation to the repeating units of polyamide (PA) means that the repeating units of the polyamide consist of (R PA1 ), (R PA2 ) and (R PA3 ) and up to 2.0 mol%, preferably up to 1.5 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol% of other than the repeating unit (R PA1 )、(R PA2 ) and (R PA3 ) other than the repeating units.

9. Polyamide (PA) according to any one of the preceding claims, wherein The proportion of 1,6-hexanediamine in the diamine component (A) or R PA1 The ratio is: - between 18.0 and 22.0 mol %; or - between 15.0 and 22.0 mol %; or - between 18.0 and 22.0 mol %.

10. Polyamide (PA) according to any one of the preceding claims, wherein The proportion of the other diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of the two diamines in the diamine component (A) or the R PA2 The ratio is: - between 18.0 and 27.0 mol %; or - between 23.0 and 27.0 mol %; - between 18.0 and 22.0 mol %.

11. Polyamide (PA) according to any one of the preceding claims, wherein The proportion of the other diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of the two diamines in the diamine component (A) or the R PA3 The ratio is: - between 50.0 and 62.0 mol %; or - between 53.0 and 62.0 mol %; or - between 53.0 and 57.0 mol %; or - between 58.0 and 62.0 wt%; or - between 61.0 and 64.0 mol%.

12. Polyamide (PA) according to any one of the preceding claims, wherein The ratios in the diamine component (A) are as follows: - between 18.0 and 22.0 mol % of 1,6-diaminohexane; - between 23.0 and 27.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 53.0 and 57.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines; or the following ratio: - between 18.0 and 22.0 mol % of 1,6-hexanediamine; - between 18.0 and 22.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 58.0 and 62.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines; or the following ratio: - between 15.0 and 20.0 mol % of 1,6-hexanediamine; - between 18.0 and 22.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 61.0 and 64.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines.

13. The polyamide (PA) according to any one of claims 6 to 12, wherein These ratios are the following: - between 18.0 and 22.0 mol% of R PA1 ; - between 23.0 and 27.0 mol% of R PA2 ; - between 53.0 and 57.0 mol% of R PA3 ; or the following ratio: - between 18.0 and 22.0 mol% of R PA1 ; - between 18.0 and 22.0 mol% of R PA2 ; - between 58.0 and 62.0 mol% of R PA3 ; or the following ratio: - between 15.0 and 20.0 mol% of R PA1 ; - between 18.0 and 22.0 mol% of R PA2 ; - between 61.0 and 64.0 mol% of R PA3 .

14. Polyamide (PA) according to any one of the preceding claims, wherein The polyamide (PA) does not comprise repeating units which are derived from lactams or from amino acids.

15. Polyamide (PA) according to any one of the preceding claims, wherein The end groups in the polyamide are selected from the group consisting of -NH2, -COOH and amide end groups, in particular those of the formula -NH-C(=O)-R, wherein R is an alkyl, aryl or cycloalkyl group, and / or in particular those of the formula -C(=O)-NH-R', wherein R' is an alkyl or cycloalkyl group.

16. Polyamide (PA) according to any one of the preceding claims, wherein The melting temperature Tm of the polyamide (PA) is: - below 285°C or below 280°C or below 270°C; and / or - at least 250°C, preferably at least 260°C; Tm is measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using heating and cooling rates of 20°C / min.

17. Polyamide (PA) according to any one of the preceding claims, wherein The glass transition temperature Tg of the polyamide (PA) is: - at least 155°C, preferably at least 165°C, preferably at least 166°C, preferably at least 167°C, preferably at least 168°C, preferably at least 169°C, preferably at least 170°C; and / or - up to 200°C or up to 180°C; Tg is measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using heating and cooling rates of 20°C / min.

18. Polyamide (PA) according to any of the preceding claims, which exhibits a difference (Tm-Tg) below 130°C, preferably below 120°C, preferably below 110°C, preferably below 100°C.

19. Polyamide (PA) according to any one of the preceding claims, which exhibits a crystallization temperature (Tc) of at most 210°C.

20. The polyamide (PA) according to any of the preceding claims, exhibiting a difference (Tm-Tc) of at least 50.0°C, preferably at least 60.0°C, preferably between 50.0°C and 75.0°C or between 50.0°C and 70.0°C, the melting temperature Tm and the crystallization temperature Tc being measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

21. The polyamide (PA) according to any one of the preceding claims, exhibiting a heat of fusion Hm of at least 15.0 J / g, preferably at least 20.0 J / g, preferably at least 25.0 J / g, Hm being measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

22. The polyamide (PA) according to any one of the preceding claims, exhibiting a heat of fusion Hm of between 15.0 and 40.0 J / g, preferably between 15.0 and 40.0 J / g (the latter value being excluded), Hm being measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

23. Polyamide (PA) according to any one of the preceding claims, exhibiting an inherent viscosity ("IV") measured according to ASTM D5336 of: - between 0.5 and 1.5 dL / g; or - between 0.7 and 1.3 dL / g; or - between 0.75 and 1.20 dL / g; or - between 0.80 and 1.00 dL / g; or - between 0.90 and 1.20 dL / g; or - Between 0.95 and 1.20 dL / g.

24. The polyamide (PA) according to any one of the preceding claims, exhibiting a number average molecular weight ("Mn") between 8,000 and 20,000 g / mol.

25. Polyamide (PA) according to any of the preceding claims, exhibiting a biocontent expressed as % of organic carbon of renewable origin determined according to ASTM D6866-22 of at least 10.0%, preferably at least 12.0%, preferably at least 60.0%.

26. The polyamide (PA) according to any one of the preceding claims, exhibiting a melt flow rate (MFR) lower than or equal to 6.0 g / 10 min, preferably lower than or equal to 5.0 g / 10 min, preferably lower than or equal to 4.0 g / 10 min, preferably lower than or equal to 3.0 g / 10 min, the MFR being measured according to ASTM D1238 at Tm+20°C using a 2.16 kg test load.

27. The polyamide (PA) according to any one of the preceding claims, prepared from 1,9-diaminononane (C9) and / or 1,10-diaminodecane (C10), exhibiting a biocontent expressed as a % of organic carbon of renewable origin determined according to ASTM D6866-22 of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%.

28. The polyamide (PA) according to any one of the preceding claims, which exhibits a water absorption at 23°C of less than 5.0 wt.%, the water absorption at 23°C being determined by: (i) providing a test specimen formed according to ISO 527 in its dry state (moisture content less than 0.2 wt.%), (ii) immersing the test specimen in deionized water at 23°C until constant weight is reached, (iii) calculating the water absorption using the following formula: Where W 之前 is the weight of the molded specimen in its initial dry state and W 之后 is the weight of the molded specimen after water absorption.

29. The polyamide (PA) according to any one of the preceding claims, prepared by polycondensation by heating a reaction mixture (RM) comprising all these monomers, the reaction mixture (RM) especially comprising or consisting of: - the monomers constituting the polyamide (PA); - optionally a catalyst, in particular chosen from the group consisting of phosphorous acid, orthophosphoric acid, metaphosphoric acid, alkali metal hypophosphites such as sodium hypophosphite, and phenylphosphinic acid, and combinations thereof; - optionally at least one capping agent selected from the group consisting of monocarboxylic acids, primary amines, and combinations thereof; - Water, in a proportion of less than 60 wt.%, preferably less than 30 wt.%, preferably less than 20 wt.%, preferably less than 10 wt.% of water, the proportion being based on the total weight of the reaction mixture (RM).

30. A thermoplastic composite (TC) comprising: a polymer matrix comprising or consisting of a polyamide (PA) according to any one of claims 1 to 28 and optionally at least one plastic additive, in particular chosen from the group consisting of: colorants, UV stabilizers, heat stabilizers, antioxidants, acid scavengers, processing aids, internal and / or external lubricants, flame retardants, smoke suppressants, antistatic agents, anti-blocking agents and any combination thereof; and -fiber.

31. Use of the polyamide (PA) according to any one of claims 1 to 28 for producing a thermoplastic composite material (TC).

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